Hydrocarbyl sulfenylmercapto pyrimidines

ABSTRACT

D R A W I N G WHEREIN R, R1 and R2 are hydrogen, halogen, hydroxy, alkyl or alkenyl optionally substituted with halogen atoms and R3 is an aliphatic hydrocarbyl group or an aryl group or WHEREIN R4 is hydrogen or alkyl and R5 is hydrogen, alkyl, alkenyl or phenyl optionally substituted with halogen atoms, and n is 0 or 1, possess fungicidal and insecticidal activity.   Compounds of the formula

United States Patent [191 Moore HYDROCARBYL SULFENYLMERCAPTO PYRIMIDKNES [75] Inventor: Joseph E. Moore, Richmond, Calif.

[73] Assignee: Chevron Research Company, San

[52] US. Cl. 260/256.5 R, 260/251 R, 424/251 [51] Int. Cl. C07d 51/40, C07d 51/38 [58] Field of Search 260/256.5 R

[56] References Cited UNITED STATES PATENTS 2,839,446 6/l 58 Margot et a1. .1 260/25l R Primary Examiner-Richard J. Gallagher Attorney, Agent, or FirmG. F. Magdeburger; John Stoner, .lr.; Raymond Owyang [111 3,821,222 [451 June 28, 1974 [57] ABSTRACT Compounds of the formula R N RKB J wherein R, R and R are hydrogen, halogen, hydroxy,

alkyl or alkenyl optionally substituted with halogen atoms and R is an aliphatic hydrocarbyl group or an aryl group or wherein R is hydrogen or alkyl and R is hydrogen, alkyl, alkenyl or phenyl optionally substituted with halogen atoms, and n is 0 or 1, possess fungicidal and insecticidal activity.

5 Claims, No Drawings HYDROCARBYL SULFENYLMERCAPTO PYRIMIDINES BACKGROUND OF THE INVENTION 1. Field The present invention is directed to hydrocarbyl sulfenylmercapto pyrimidines and their use as fungicides and juvenile hormone mimetic insecticides.

2. Prior Art US. Pat. No. 2,839,446 discloses certain pyrimidine derivatives, particularly trichloromcthyl sulfenylmercapto pyrimidines and their use in the control of fungi.

DESCRIPTION OF THE INVENTION The present invention is directed to certain novel pyrimidine compounds and the use of certain pyrimidine compounds for the control of fungi and insects. Certain of the pyrimidines mimic the activity of juvenile hormone.

The novel compounds of the present invention can be represented by the general formula wherein R, R and R are individually hydrogen, halogen of atomic number 9 to 35 (fluorine, chlorine or bromine), hydroxy, alkyl of l to 6 carbon atoms substituted with to 4 halogen atoms of atomic number 9 to 35 or alkenyl of 2 to 6 carbon atoms substituted with 0 to 4 halogen atoms of atomic number 9 to 35, R is an aliphatic hydrocarbyl group (i.e., alkyl or alkenyl) of 2 to 10 carbon atoms substituted with l to 5 halogen atoms of atomic number 9 to 35, aryl of 6 to 12 carbon atoms substituted with 0 to 2 halogen atoms of atomic number 9 to 35 or alkyl groups of l to 4 carbon atoms,

wherein R is hydrogen or alkyl of.1 to 4 carbon atoms and R is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms or phenyl substituted with O to 2 halogen atoms of atomic number 9 to 35, and n is 0 or 1.

Preferably R is hydrogen, R and R are, individually, hydrogen, hydroxy or alkyl of 1 to 4 carbon atoms and R is alkyl of 2 to 4 carbon atoms substituted with l to 5 halogen atoms of atomic number 9 to 35, particularly chlorine, or phenyl substituted with 0 to 2 halogen atoms of atomic number 9 to 35, particularly chlorine,

wherein R is alkyl of l to 4 carbon atoms and R is hydrogen. More preferably, R is hydrogen or methyl, R is hydrogen, R is hydrogen, hydroxy or alkyl of l to 3 carbon atoms and R is alkyl of 2 to 4 carbon atoms substituted with 2 to 5 chlorine atoms or phenyl substituted with 1 to 2 chlorine atoms. The most preferred R groups are the tetrachloroethyl, l,l-dimethyl-2,2- dichloroethyl, p-chlorophenyl or wherein R is ethyl and R is hydrogen.

- The above novel compounds are useful in the control of fungi. Also, the above novel compounds are useful insecticides. In fact, the compounds described above possess juvenile hormone mimetic activity. In particular the compounds wherein R is an aliphatic hydrocarbyl group of l to 10 carbon atoms substituted with l to 5 halogen atoms of atomic number 9 to 35 possess juvenile hormone mimetic activity. Thus compounds wherein R is methyl substituted with halogen atoms also have juvenile hormone mimetic activity.

Representative compounds which R, R and R may represent are hydrogen, fluorine, chlorine, bromine, hydroxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, pentyl, hexyl, allyl, crotyl, 2- propenyl, chloromethyl, trichloromethyl, bromomethyl, 2-fluoroethyl, etc.

Preferably the representative groupsfor R, R and R will be hydrogen, hydroxy, methyl, ethyl, propyl and butyl.

Representative groups which R may represent include l-chloroethyl, 1,1-dichloroethyl, 1,1,2- trichloroethyl, 2,2,2-trichloroethyl, 1,1 ,2,2-tetrachloroethyl, l,2,2,2-tetrachloroethyl, pentachloroethyl, trichlorovinyl, ethyl, l, l -dimethyl-2,2-dichloroethyl, l,l,2,2-tetrachloropropyl, 1,2,3-trichloropropyl, l, l -difluoroethyl, l ,1 ,2-tribromoethyl, l-bromo-Z-chloroethyl, l ldichlorohexyl, phenyl, naphthyl, 4-chlorophenyl, 2- chlorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl,- 2-bromophenyl, 3-fluorophenyl, 2-methyl-4- chlorophenyl, 4-butyl-phenyl, etc.

Representative groups which R may represent include methyl, ethyl, n-propyl, isopropyl, n-butyl, tbutyl, etc.

Representative groups which R may represent include hydrogen, methyl, ethyl, propyl, butyl, allyl, vinyl, phenyl, o-chlorophenyl, o,p-difluorophenyl, etc.

When the compounds are used as insecticides, R may also represent chloromethyl, dichloromethyl, trichloromethyl, bromochloromethyl, trifluoromethyl, dibromomethyl, etc.

Typical compounds of the present invention include the following: 2-( l, l ,2,2- tetrachloroethylsulfenylmercapto)-4-methyl .pyrimidine, 2-( 1,1,2,2-tetrachloroethylsulfenylmercapto)-4- chloromethyl-6-hydroxy pyrimidine, 2-( 1 l ,2 ,2- tetrachloroethylsulfenylmercapto)-4,6-dimethyl pyrimidine, 2-( 1 ,l ,2,Z-tetrachloroethylsulfenylmercapto)-4-chloro pyrimidine, 2-( 1,1 ,2,2- tetrachloroethylsulfenylmercapto)-4,5,-trimethyl pyrimidine, 2-( 1,1,2,2-tetrachloroethylsulfenylmercapto)-4-hydroxy pyrimidine, 2-( 1,1 ,2,2-

l, 1 -dimethyl-2,2,2-trichloro- 3 tetrachloroethylsulfenylmercapto )-4-hydroxy-6- methyl pyrimidine, 2-( l ,l ,2,2-

pyrimidine, 2-trichlorovinylsulfenylmercapto-4,6- dimethyl pyrimidine, 2-(1,2- dichlorovinylsulfenylmercapto )-4,6-diethyl pyrimidine, 2-( 1 l ,2,2-tetrachloropropylsulfenylmercapto 4-hydroxy pyrimidine, 2-(l,2,3-trichloropropylsulfenylmercapto) pyrimidine, 2-(1,2,3- trichloropropylsulfenylmercapto)-6-ethyl pyrimidine, 2-pentachloroethylsulfenylmercapto-4-methyl-6- isopropyl pyrimidine, 2-( l 1 -dimethyl-2,2- dichloroethylsulfenylmercapto)-4-propyl pyrimidine, 2-( l ,1-dimethyl-2,2-dichloroethylsulfenylmercapto)-4- hydroxy-6-methy1 pyrimidine, 2-( 1, 1 -dimethyl-2,2- dibromoethylsulfenylmercapto)-4-butyl pyrimidine, 2-( l l ,2,2-tetrachloroethylsulfenylmercapto) pyrimidine, 2-(phenylsulfenylmercapto)-4,5-dimethyl pyrimidine, 2-(4-chlorophenylsulfenylmercapto)-4-methyl-6- hydroxy pyrimidine, 2-(4-ehlorophenylsulfenylmercapto)-4-ethyl pyrimidine, 2-(4-chlorophenylsulfenylmercapto)-6-hydroxy pyrimidine, 2-(4- chlorophenylsulfenylmercapto )-4,5 ,6-trimethyl pyrimidine, 2-(4-chlorophenylsulfenylmercapto)-4-allyl pyrimidine, 2-(3,4-dichlorophenylsulfenylmercapto)-4- methyl 6hydroxy pyrimidine, 2-( 3- methylpehnylsulfenylmercapto)-4-hydroxy-6-methyl pyrimidine, 2-(2-fluoro-4- chlorophenylsulfenylmercapto)-4-methyl pyrimidine, 2-( 2-methyl-4-ehlorophenylsulfenylmercapto )-4- hydroxy pyrimidine, trichloromethylsulfenylmercapto)-4-hydroxy-6-methyl pyrimidine, N-ethyl-N-(4,6-dimethylpyrimido-2-sulfenylmercapto) formamide, N-methyl-N-(4-hydroxy-6- methylpyrimido-2-sulfenylmercapto) formamide, N- propyl-N-(4-ethyl-6-vinylpyrimido-Z-sulfenylmercapto) formamide, N-ethyl-N-(4,6-dimethylpyrimido- 2-sulfenylmercapto) acetamide, N-methyl-N-(4- hydroxy-6-chloropyrimido-2-sulfenylmercapto) benzamide, etc.

The hydrochlorides of the above-named compounds are also included.

The compounds of this invention are prepared by the reaction of a halogenated hydrocarbyl sulfenylchloride or an amide sulfenylchloride and an appropriate 2- mercapto pyrimidine or Z-mercapto pyrimidine hydrochloride. The reaction may be written as follows:

wherein R, R, R and R are as previously defined. When the 2-mercapto pyrimidine starting material is the hydrochloride salt two moles of hydrogen chloride are released during the reaction.

The reaction is usually carried out in a solvent. The reaction involving 2-mercapto pyrimidine may be carried out in dichloromethane, chloroform, benzene, xylene, ethyl acetate or a liquid carboxylic acid. The reaction involving a Z-mercapto pyrimidine hydrochloride is preferably carried out in acetic acid as the solvent. The quantity of solvent is not critical and generally varies in weight from 5 to 50 times the weight of the pyrimidine compound. Usually the pyrimidine compound is dissolved or slurried in the solvent, and then unsolvated halogenated hydrocarbyl sulfenyl'chloride in an amount at least equal in moles to the pyrimidine is added rapidly. The reaction temperature may vary from 20 to 100C. In order to completely remove the byproduct hydrogen chloride, a temperature of to 100C. is preferred. When a hydrochloride product is desired, the reaction temperature is kept lower, e.g., below C. The time of reaction is dependent upon the temperature and the nature of the reactants; however, reaction is continued until all of the insoluble starting material has disappeared. Usually the reaction is complete in from 0.1 to 10 hours, more often 0.5 to 1 hour.

The product is recovered from the reaction mixture by filtering hot and then evaporating off the solvent. The resulting crude product may be used as is, or it may be purified by crystallization or by chromatography. Crystallization is readily accomplished by cooling a solution of the crude product. Solvents for crystallization are preferably mixtures of aromatic hydrocarbons such as benzene, toluene, etc. with an aliphatic hydrocarbon such as pentane, hexane, etc. The ratio of the two may vary from 1:2 to 2:1 by volume.

The compounds of this invention may also be prepared by the process of U.S. Pat. No. 2,839,446, which is concerned with the 2-trichloromethyl sulfenylmercapto pyrimidines.

The subject invention can be more fully understood by reference to the following examples. Unless otherwise indicated percentages are by weight.

EXAMPLE 1 Preparation of 2-( l l ,2,2-tetrachloroethylsulfenylmercapto)-4-methyl pyrimidine A suspension was prepared by mixing 3.4 g. (0.02 mole) 2-mercapto-4-methyl pyrimidine hydrochloride in ml. of acetic acid. Then 5.0 g. (0.02 mole) of tetrachloroethylsulfenylchloride was added to this suspension all at once. The resulting mixture was stirred at the reflux temperature for three minutes. At the end of this time the reaction mixture was filtered while hot. The filtrate was evaporated to 10 ml. of volume. This material was then diluted with 100 ml. of benzene and 75 ml. of hexane and cooled to 0C. The precipitate was removed by filtration and discarded. The filtrate was evaporated to give a liquid which crystallized upon standing. The crystals were separated by filtration and after drying weighed 3.3 g. The product, 2-(1,l,2,2- tetrachloroethylsulfenylmercapto)-4-methyl pyrimidine, had a melting point of 54- 56C. Analysis was as follows:

Calculated Found Infrared analysis showed strong adsorption bands at 6.15, 6.35, 6.75, 7.2, 7.65, 11.7, 12.4 and 13.3 mic1 '7 43 s 43 2 Crons' S i Other compounds of the present invention were 5 made by s rnilar reactions. These are listed in Table TABLE I Elemental Analysis 7r Melting Calculated Fo d Point Compound Cl N S Cl N S C.

2-(4-chlorophenylsulfcnylmcrcapto)- 13.2 23.8 14.4 23.1 80-82 4-methyl pyrimidine 2-(1,2,2,2-tetrachloroethylsulfenyl- 45.7 20.1 45.4 20.5 51 mercapto) pyrimidine 2-(1,1,2.2 tetrachloroethylsulfenyl- 45.7 20.1 46.3 20.5 89-90 mercapto) pyrimidine 2-(1,1,2,Z-tetrachloroethylsulfenyl- 8.3 7.6 53-54 mercapto)-4,6-dimethyl pyrimidine 2-(1,1-dimethyl-2,2-dich1oroethyl 33.1 20.0 29.6 19.4 200 sulfenylmercapto)-6-hydroxy pyrimidine (dec) hydrochloride 2-( l,1-dimethy1-2,Z-dichloroethyl- 23.9 21.6 24.4 21.6 82.5-83.5 sulfenylmercapto)-4,6-dimethyl pyrimidine 2-(1,1-dimethyl-2,2-dichloroethyl-sulfenyl- 17.6 29.6 17.5 W 29.5 "ill-T? mercapto)-4-propyl-6-hydroxy pyrimidine (dec) hydrochloride A 2-(1,1,2,Z-tetrachloroethylsuflafi; 48.9 17.1 47.1 17.0 1 16-126 'Wmidine V hydrochloride 7 2-(1,2,2,2-tetrachloroethylsulfenyl- 43 .77 19.79 43 .60 18.65 Oil mercapto)-4-methyl pyrimidine W 2-(1 ,l-dimethyl-Z, 2dichlorosulfenyl- 25.04 22.64 26.75 21.48 Oil mercapto) 4-methyl pyrimidine m 7 7M N-ethyl-N-4,6-dimethylpyrimido-Z-sulfenyl- 1 V 0 17.3 26.4 Oil mercapto) formamide The infrared spectra had strong adsorption bands at UTILITY 6.35, 6.8, 7.5, 8.3, 12.0, 12.45, 13.2 and 14.05 microns EXAMPLE 2 Preparation of 2-( 1, I ,2,2-tetrachloroethylsulfenylmercapto)-4- hydroxy-6-propyl pyrimidine hydrochloride To a slurry of 5.0 g. (0.029 mole) of 2-mercapto-4-. hydroxy-6-propyl pyrimidine in 50 ml. of 1,2- dimethoxyethane, was added 6.9 g. (0.029 mole) of l,- 1,2,2-tetrachloroethylsulfenylchloride. The resulting The novel compounds of the present invention exhibit fungicidal activity against a variety of fungi. The following examples indicate the fungicidal activity.

Example A The inventive compounds were evaluated for fungicidal effectiveness by means of the mycelial drop test.

50 This test is designed to measure the fungitoxic activity of fungicidal chemicals in terms of their degree of inhibition on mycelium growth. Each compound to be tested was dissolved in acetone to 250 ppm concentration. Paper discs previously inoculated with equal mixture was heated at the reflux temperature for ten amounts of particular fungus mycelium were placed on pyrimidine hydrochloride having a melting point of l42-l44C. Analysis was as follows:

Calculated Found Cl 7: 43.8 43.0 S 7: 15.8 15.5

potato dextrose agar medium. The paper discs were treated by applying a precise and equal volume of each of these fungicidal solutions to the center. Following treatment with the fungitoxic chemical. the discs were incubated along with inoculated but untreated control discs at ambient temperatures until such time that the mycelial growth away from the edge of the untreated control discs reached a certain distance. From this comparison a percent inhibition of growth area was de-v termined. The results of these tests for various compounds of this invention on the particular fungus mycelium are indicated in Table II.

TABLE H W 7: Control Pythium ilmlnthosporium Fusarium Rhizoctonia Compound ultimum sativum" T oxysporum l i 2-( l,l,2,2-tetrachloroethylsulfenyl- 96 98 78 100 mercapto)-4-methyl pyrimidine 2-( i,l,2,Z-tetrachloroethylsulfenyll3 I mercapto)-4-hydroxy-6-propyi pyrimidine hydrochloride 2-( l2,2.2-tetrachlomethylsulfenyl- 78 mercapto) pyrimidine 2-( l.l,2,2-tetrachloroethylsulfenyh 100 99 99 I00 mcrcapto) pyrimidine 2-( 1.1 ,2,2-ietrachloroethylsulfenyl- I00 99 100 mereapto)-4,6-dimcthyl pyrimidine u 2-( l.l-dimelhyl-2.2-dichloroethyl- 9O sulfenylmercapto)-4.6-dimethyl pyrimidine 2-( l,l-dimethyl-2,2-dichloroethyl 85 sulfenylmercapto)-4-propyl-6-hydroxy pyrimidine hydrochloride 2-( l ,2,2,2-tetrachloroethylsulfenyl- 78 mercapto)-4-methyl pyrimidine N-methyl-N-(4,6-dimethylpyrimido-2- 78 70 sulfenylmereapto) formamide 2-( l,l.2,2-tetrachloroethylsulfenyllOO 70 mercapto)-6hydroxy pyrimidine hydrochloride EXAMPLE B A number of the compounds were also tested for effectiveness against spores by means of a variation of The Standard Spore Slide-Germination Method for' Determining Fungicidal Activity," described in the American Phyto mtlzological Society Journal, Volume 33, pages 627-632 (I943). The method is designed to measure the fungitoxic activity of fungicidal chemicals, their activity being expressed in terms of percent inhibition of germination of fungus spores. Each compound toxicant to be tested was dissolved in acetone to a concentration of 100 ppm. These solutions were then pipetted into the wells of depression slides and allowed to dry. The wells were filled with a spore suspension of the specified test organism. A -fold greater volume of suspension was used than that used to apply the toxicant so that the slide concentration of toxicant was 10 ppm. The spores were then incubated in a moist chamber overnight. A group of 100 spores was examined and the number of spores germinated and not germinated was counted and recorded to show the biological activity in terms of the percent germination inhibition. Table III reports the results of this testing.

sulfenylmercapto) formamide When used as fungicides the compounds of this invention will be formulated and applied in fungicidal amounts by conventional art methods to fungi or hosts which are subject to fungus attack, especially vegetative hosts such as plants, plant seeds, etc. The amount used will, of course, depend upon several factors such 'as the host, the type of fungus, the particular compound, etc. The amount generally will range from 2 to The compounds may be combined with inert liquids or solid carriers as powders, solutions, dispersions, etc. for such use.

The compounds of this invention will generally be admixed with biologically inert liquids or solids in an amount of from about 0.005 to weight percent. Higher or lower amounts can be used to advantage. Preferably from 1 to 50 weight percent of the composition will be the compound. Typical of the liquid carrier which may be admixed with the compounds of this invention include, in addition to acetone, such liquids as water, kerosene, xylene, alcohols, alkylated naphthylene and glycols. Typical solids which may be incorporated with' the compounds includethe natural clays, such as kaolin clays, diatomaceous earth, synthetic fine silica, talc, pyrophyllite, etc.

Fungicidal formulations may also contain stabilizers,

spreading agents, sticking agents, fillers, other compatible pesticides and the like.

The compounds of the present invention also exhibit insecticidal activity, particularly juvenile hormone mimetic activity. The following tests were conducted to show the juvenile hormone activity.

EXAMPLE c Tests were carried out on the following pests: Dock Beetle (Gastrophysa cyanes), Cabbage Looper (Trichoplusia ni) and Yellow Fever Mosquito (Aedes aegypti).

For the Dock Beetle test, an acetone solution con- 5 kept in an incubator until the adult emerged (or attempted to emerge). At this time a count was made of the dead pupae. The live specimens were examined under a microscope for juvenilization. The number of juvenile adults per-total number testcdwas recorded, and is given in Table IV as percent juvenilization. Also the degree of juvenilization was measured based on the following:

O normal appearing adult 1=crumpled elytra in the adult 2=V2 pupa /2 adult 3=supernumery pupa 4=% larva /2 pupa Percent control, defined as the percentage of treated insects which failed to perpetuate themselves, was also measured. in determining percent control, account was made of treated insects that failed to reach adulthood for one reason or another, plus those that failed to lay eggs, or that layed sterile eggs.

For the Cabbage Looper, an acetone solution con- 30 taming 100 micrograms of the test compound in 5 microliters of solution was applied topically to the entire length of the body of a late fifth stage larva. Normally 10 larvae were treated per test. The treated larvae were then fed until they pupatecl. The pupae were examined under a microscope, checking for any larvae characteristics in the pupae (juvenilization). Percent juvenilization as well as mortality readings were made. The pupae were incubated until the adult (if any) emerged. These adults were then checked as to egg laying and percent laying fertile eggs. Mortality of the adults was determined. Juvenilization, degree of juvenilization and percent control were determined. The degree of juvenilization was measured based on the following:

0=normal appearingpupa l=% larva /z pupa; no prolegs; pupoid thorax =/2 larva pupa; prolegs; purpoid thorax M 3=superr 1trmery larva For the Yellow Fever Mosquito, late fourth stage larvae of the mosquitos were placed in a cup containing ml. of deionized water having 6 ppm of the test material dissolved therein. About 20 larvae were used per test. The larvae were fed and allowed to pupate. The pupae were examined under a microscope for retention of larvae characteristics (juvenilization). The live pupae were kept until the adult mosquito emerged, mated and layed eggs. The percent fertile eggs was determined. A count was made at each stage for mortality, i.e. larvae pupae and adult.

The results of the tests are tabulated in Table IV.

TABLE IV Dock Beetle Cabbage Longer xellow Fever Mosggito .luve- Juvel .Iuvenilinilinili Cone. zation Con- Conc. zation Conzation Con- (;A g/ trol ([1. g/ trol Conc. trol Compound insect) (Degree) (1) insect) (Degree) (1) (ppm) (Degree) (1) 2-( 1.1.2.2-tetruchloro- (4) 10 30 (1.6) 6.6 0(0) 100 cthylsult'cnylmcrcupto)- 4-mcthyl pyrimidine 2-(1.1.2.2-tetruchloro- I00 (I 70 ctliylnulfunylmercnptu)-4- hydroxy-o-pmpyl pyrimidine hydrochlorodc 2-(1.2.2.2-tetrachloro-ethylsulfenyl- 20 I00 20(1) 100 mercapto)pyrimidine 2-(1,1,2,Z-tetrachloroethylsulfenyl- 100 9( 0.

mercapto)pyn'midine 2-(1,1,2,Z-tetrachloro-ethylsulfenyl 20 60 30 100(15) 100 15 O() 90 mercapto)-4,5-dimethyl pyrimidine 2-(1,1-dimethyl-2,Z-dichloroethyl- 2O 50 250 h 30 sulfenylmercapto)-4,6-dimethy1 pyrimidine 2-(1,1,2,Z-tetrachloroethylsulfenyl- 20 10(2) 100 mercapto)-6-hydroxy pyrimidine hydrochloride 1 2-(1,2.2,Z-tetrachloroethylsulfenylv 100 20(1) 40 mercapto)-4-methy1 pyrimidine N-methyl-N-(4,6-dimethylpyrimido-2- 20 '0(- 90 100 60(1) 100 sulfenylmercapto)formamide 2-(trichloromethyl-sulfenylmercapto)-4- 30 50(1) 50 v methyl pyrimidine (1) Percent control refers to the perce ntage of treated insects that failed to reach adulthood for any reason, plus those that failed to lay eggs, plus those that layed sterile eggs; in effect, the percent treated insects that failed to perpetuate themselves.

When used as an insecticide the compounds may be applied in either liquid or solid formulations to the insects, their environment or hosts susceptible to insect attack. For example, they may be sprayed or otherwise applied directly to plants or soil so as to effect control of insects coming into contact therewith.

Formulations of the compounds of this invention will comprise a toxic amount of one or more of the compounds and a biologically inert carrier. Usually they will also contain a wetting agent. Solid carriers such as clay, talc, sawdust and the like may be used in such formulations. Liquid diluents which may be used with these compounds include water and aromatic solvents. In addition these formulations may contain other compatible pesticides, fillers, stabilizers, attractants and the like.

The concentration of the active ingredient to be used with inert carriers, either solid or liquid carriers, will be dependent upon many factors, such as the particular compound which is used, the carrier in or upon which it is incorporated, the method and conditions of application, the insect species to be controlled, etc., the proper consideration of these factors being within the skill of those versed in the art. In general, the toxic ingredients of this invention will be effective in concentrations from about 0.0001 percent by weight to as high as 50 percent by weight or higher. Economically, of course, it is desirable to use lower concentration of this active ingredient. Thus, it is usually desirable to use less than 20 percent by weight of the active ingredient in a particular composition.

The terms insecticide and insect as used herein refer to their broad and commonly understood usage rather than to those creatures which in the strict biological sense are classified as insects. Thus, the term insect is used not only to include small invertebrate animals belonging to the class lnsecta but also to other related classes of arthropods whose members are segmented invertebrates having more or fewer than six legs, such as spiders, mites, ticks, centipedes, worms and the like.

wherein R is hydrogen, R and R are individually hydrogen, hydroxy or alkyl of 1 to 4 carbon atoms, and R is wherein R is hydrogen or alkyl of 1 to 4 carbon atoms and R is hydrogen, alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 4 carbon atoms or phenyl substituted with ,0 to 2 halogen atoms of atomic number 9 to 35, and n is 0 or 1.

2. Compound of claim 1 wherein R is alkyl of l to 4 carbon atoms and R is hydrogen or alkyl of l to 4 carbon atoms.

3. Compound of claim 2 wherein R is hydrogen or methyl, R is hydrogen, hydroxy or alkyl of 1 to 3 carbon atoms, R is ethyl and R is hydrogen.

4. Compound of claim 2 wherein R is hydrogen and n is 0.

5. Compound of claim 4, being N-ethyl-N-(4,6-

dimethylpyrimido-2-sulfenylmercapto)formamidc.

. UNITED STATES PATENT" OFFICE 4 CERTIFICATE OF CORRECTION Patent No. 3,821,222 Dated June 28, 1974 On preamble page, in the Abstract, formula should read 1 lnvento JOSEPH E. MOORE It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 1, linev 27, formula should read N Table III, heading of last column, delete "Alter" and insert in lieu thereof -Alterneria-. 1

Table IV, Col. 1, Fifth Compound, second line, "4,5-" should C01. 12, line 12, formula should read I| |I Col. 3, line 42, "pehnyl" should read -phenyl-.

Col. 4, line 59, "of" should read --by-.

Table II, second cola under "Pythium ultimum" "13'' should read Col. 10, line 17, "purpoid" should read pupoid-."

Table IV, Second Compound, "hydrochlorode" should read -hydrochloride--.*

Table IV, Col. 2, Third Compound, "20" should read Signed and. sealed this 5th day of November 1974.

(SEAL) Attest:

McCOY GIBSON JR, I, C. MARSHALL DANN Attestlng Officer Commissioner of Patents 

2. Compound of claim 1 wherein R4 is alkyl of 1 to 4 carbon atoms and R5 is hydrogen or alkyl of 1 to 4 carbon atoms.
 3. Compound of claim 2 wherein R is hydrogen or methyl, R2 is hydrogen, hydroxy or alkyl of 1 to 3 carbon atoms, R4 is ethyl and R5 is hydrogen.
 4. Compound of claim 2 wherein R5 is hydrogen and n is
 0. 5. Compound of claim 4, being N-ethyl-N-(4,6-dimethylpyrimido-2-sulfenylmercapto)formamide. 